Synthetic Metals 159 (2009) 1837–1843

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Effect of synthesis conditions on the properties of wet spun polypyrrole fibres

Javad Foroughi, Geoffrey M. Spinks, Gordon G. Wallace ∗
ARC Centre of Excellence for Electromaterials Science, Intelligent Polymer Research Institute, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522, Australia

a r t i c l e i n f o a b s t r a c t

Article history: High molecular weight doped polypyrrole (PPy) has been synthesized by the incorporation of the di(2-
Received 15 December 2008 ethylhexyl) sulfosuccinate dopant anion which renders the polymer soluble in various organic solvents.
Received in revised form 5 June 2009 The intrinsic viscosity of PPy solutions show that the molecular weight of PPy is very sensitive to the
Accepted 5 June 2009
polymerization temperature. A significant increase in molecular weight was achieved by reducing the
Available online 10 July 2009
polymerization temperature from 0 to −15 ◦ C. The resultant solutions were amenable to a wet-spinning
process that produced continuous, doped polypyrrole fibres. The ultimate tensile strength, elastic mod-
Keywords:
ulus and elongation at break of the higher molecular weight fibres were 136 MPa, 4.2 GPa and 5%,
Polypyrrole
Fibre
respectively. These values were 500%, 250% and 280% higher than obtained from the lower molecular
Wet spinning weight fibers. X-ray diffraction showed that the low temperature PPy powder exhibited a similar degree
Conducting polymer of ordering to the standard PPy powder. UV and FT-IR spectroscopy showed that the conjugation length
Electronic textile of PPy could be increased significantly depending on the polymerization conditions. Cyclic voltamme-
try demonstrated the electroactivity of the polypyrrole fibres. These fibres are likely to be important for
bionic, electronic textile, artificial muscles, battery and sensor applications.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Although polymers dominate the general fibre and textile indus-
tries they have had little impact on applications that require
electrically conducting or electronic properties. Conducting poly-
mer fibres are likely to be important for electronic textile
applications as they allow the possibility to incorporate desirable
features like chemical sensing or actuation that are not feasible with
metallic fibres. However, the production of continuous conducting
polymer fibres has proved difficult as their common forms are not
soluble, and cannot be processed by melt techniques like extrusion.
Some success was previously achieved using polyaniline, however,
polyaniline is less environmentally stable, less biocompatible and
produces limited actuation compared to polypyrrole. Polypyrrole
(PPy) is a well known conducting polymer that is already used in
a range of applications including battery electrodes [1], gas sen-
sors [2], biological sensors [3], ion-sieving, corrosion protection [4],
microwave shielding [5,6], e-Textiles and artificial muscles [1,7–12].
In addition, polypyrrole manufactured by conventional chemical
and electrochemical methods is normally insoluble in ordinary
organic solvents [13] and this intractability has been attributed to
the presence of strong interchain interactions [14]. Consequently,
PPy films are normally prepared electrochemically with the size of
the film restricted to the electrode area, although slow production
∗ Corresponding author. Tel.: +61 2 42213127; fax: +61 2 42213114.
E-mail address: gwallace@uow.edu.au (G.G. Wallace).
of PPy tape has been demonstrated using a rotating anode apparatus
[15].
Recently the availability of soluble PPy [16] has enabled the
production of PPy fibres for the first time [17]. The incorporation
of di(2-ethylhexyl) sulfosuccinate (DEHS) dopant anion renders
the polymer soluble in polar and also weakly polar or non-polar
solvents such as n-methyl pyrrolidine (NMP), dimethyl sulfoxide
(DMSO), dimethyl formamide (DMF) and m-cresol [16]. The inter-
action of the DEHS dopant with doped PPy chains is illustrated in
Scheme 1. The first PPy fibres were found to show adequate conduc-
tivity (1–3 S cm−1 ) and were moderately electroactive. The fibres,
however, were brittle which limited their applicability.
Increasing the molecular weight of soluble PPy is one of the
most likely ways to improve the properties of the PPy fibres. In
previous work it was found that oxidant concentration, polymer-
ization temperature, and polymerization time are the key factors
that determine the molecular weight and resultant electrical con-
ductivity and solubility of the PPy-DBSA (dodecylbenzenesulfonic
acid) [18]. The electrical conductivity of PPy-DBSA increased with
increasing oxidant concentration and with decreasing polymer-
ization temperature [18]. The increased conductivity obtained by
polymerization of PPy at lower temperature and with higher oxi-
dant/monomer (pyrrole) mole ratio was caused by the increased
number of radical cations of PPy monomer or oligomer resulting
from the raised oxidant concentration, which increased the PPy
chain length. Furthermore, polymerization temperature controls
the reaction rate, which should be slowed down to obtain a molec-
ular structure with high linearity. In addition, it was reported that

0379-6779/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2009.06.006
1838 J. Foroughi et al. / Synthetic Metals 159 (2009) 1837–1843
Scheme 1. Schematic diagram showing interaction between DEHS− and oxidised
polypyrrole.
polymerization time significantly affected the electrical conduc-
tivity and solubility of the PPy-DBSA. Doping level as well as the
apparent yield, defined as the ratio of PPy-DBSA/monomer feed,
increased with increasing polymerization time over the range from
5 min to 4 h. However, longer polymerization times produced little
increase in the doping level [18].
Based on these prior studies, the polymerization conditions
were further modified in an attempt to produce high molecular
weight PPy-DEHS that could be wet spun into fibres. The aim of the
current study was to prepare PPy-DEHS fibres from polymer pro-
duced at low polymerization temperatures and to characterize the
structure and properties of the polymer and fibres formed.
2. Experimental
2.1. Materials
Di-(2-ethylhexyl) sulfosuccinate sodium salt (Na+ DEHS− ),
ammonium peroxydisulfate (APS), dichloroacetic acid (DCAA, 98%),
and dimethylformamide (DMF) were supplied by Sigma–Aldrich
and used as received. Pyrrole monomer (95%, Aldrich) was used
after distillation.
2.2. Polypyrrole synthesis
Pyrrole (0.4 M) and DEHS (0.15 M) were mixed in distilled water
(400 ml) including 20% (v/v) ethanol to reduce the freezing point.
The solution was prepared with mechanical stirring and cooled
to −15 ◦ C. APS (0.2 M) dissolved in 100 ml distilled water was
added during ∼15 min with mechanical stirring to the pyrrole/DEHS
solution. The reaction mixture was held at −15 ◦ C for 24 h with
mechanical stirring. The precipitate of DEHS doped PPy was washed
several times with distilled water then purified by centrifugation at
4000 rpm for 20 min. The resultant wet PPy powder (65% by weight
of polymer) was stored at −30 ◦ C before use because it was found
that the solubility of dried PPy was decreased significantly. PPy-
DEHS prepared as above is referred to here as “low temperature
PPy-DEHS”, while the term “standard PPy-DEHS” refers to polymer
prepared at 0 ◦ C using previously described methods [17]. For fur-
ther comparison purposes, a third polymer was synthesized using
the standard method at 0 ◦ C but without the DEHS dopant.
2.3. Fibre spinning
The fibre spinning solution was prepared by slowly adding 2.5 g
of wet PPy (65% PPy) to 10 g DCAA over a period of 1 h with vig-
orously stirring. The spinning solution was stirred for another 2 h
(200 rpm) at 20 ◦ C. Finally, a further 1 h of stirring under a dynamic
vacuum ensured a bubble free solution ready for fibre spinning.
Prior to spinning, the solution was passed through a 200 ␮m
filter using a nitrogen (N2 ) pressure vessel. The filtered solution was
transferred to a syringe and a syringe pump was used to drive the
spinning solution through a single hole spinneret with D = 400 ␮m
and finally to the coagulation bath. The bath contained 40% (v/v)
DMF in water at 20 ◦ C. The syringe pump was adjusted to 100 ml/h
to control the injection rate for the spinning dope. The fibre was
held in the coagulation bath for 30 min, where the fibre solidified.
The fibre was then kept for 24 h in a water bath to reduce the solvent
content, and then for 24 h in air at room temperature.
In some cases the fibre was further treated by hot drawing. A
dynamic mechanical analyzer (DMA, TA Instruments) was used to
heat the fibre to 100 ◦ C and then stretch the fibre to the desired
strain (without breakage). Such drawn fibres were cooled and fur-
ther evaluated.
2.4. Instrumentation
For electron microscopy, fibre samples were cut after cooling in
liquid N2 to obtain circular undamaged cross-sections. Small pieces
of fibre were fixed vertically on an aluminum stub using conduc-
tive glue. A sputter coater (Dynavac) was used for coating a thin
layer of gold on the cross-section and side wall of the fibres (35 mA
for 12 s under 200 mbar Ar). A Leica Stereoscan 440 Scanning Elec-
tron Microscope (SEM) was used for morphological studies of the
fibres.
Tensile testing was carried out using TA Instruments DMA. For
tensile testing, a 10 mm gauge length of fibre was stretched at 25 ◦ C
and at a strain rate of 500 ␮m/min until the sample failed.
The electrical conductivity of the fibres was measured using an
in-house built four point probe. The electrodes consisted of four
parallel rods at a spacing of 0.33 cm; the fibres were connected
to the parallel rods using silver paint (obtained from SPI). A con-
stant current was applied between the two outer electrodes using a
Potentiostat/Galvanostat (Princeton Applied Research Model 363).
The potential difference between the inner electrodes was recorded
using a digital multimeter 34401A (Agilent).
The dynamic solvation diameter of PPy dispersions in DCAA
were measured using dynamic light scattering (ZS, Malvern, UK).
A red laser beam of 632 nm (He/Ne) was used. This system uses
the NIBS (non-invasive back scatter) technology where the back
scatter at 173◦ is detected. The use of NIBS technology reduces mul-
tiple scattering effects since scattered light does not have to travel
through the entire sample, so that the size distribution at higher
concentrations of sample can be measured.
A three electrode electrochemical cylindrical cell
(15 mm × 50 mm) coupled to a Bioanalytical Systems (Model
CV27) potentiostat was used for cyclic voltammetry. A 10 mm
fibre was used as the working electrode with an Ag/AgCl reference
electrode and a Pt mesh counter electrode.
Viscometry measurements were performed using an Ubbelohde
type viscometer from Cannon Instrument Co. The temperature of
the viscometer was maintained by immersing the apparatus in a
constant-temperature water bath regulated by Julabo temperature
controller. The viscosity of the spinning solution was also recorded
using an Anton Paar viscometer (physical MCR 301) using Rheoplus
software.
X-ray diffraction was performed using a GBC-MMA diffractome-
ter with Cu K␣ radiation and graphite monochromator. Powder and
fibre samples were dispersed on the surface of glass substrates. The
long axis of the fibres was made parallel to the beam direction.
Ultra violet–visible–near infrared spectra were obtained using a
Cary 5000 spectrophotometer. The TGA characteristics of PPy pow-
der, fibres and dopant (DEHS) were studied from room temperature
 J. Foroughi et al. / Synthetic Metals 159 (2009) 1837–1843
Fig. 1. UV–VIS/NIR spectra of dilute solution (0.01%, w/w) of low temperature PPy-
DEHS in solvent (DCAA).
Fig. 2. The size distribution obtained by light scattering of dilute solution (0.01%,
w/w) of low temperature PPy and standard PPy in DCAA as labeled.
to 600 ◦ C (TA Instrument Q500 thermal gravimetric analyzer) at a
heating rate of 5 ◦ C/min in a nitrogen purge.
3. Results and discussion
3.1. Characterisation of polymer structure
The UV–VIS/NIR spectra of PPy dissolved in dichloroacetic acid
was measured in the range from 300 to 2100 nm (Fig. 1). A strong
absorption peak at 420 nm assigned as –* transition and a very
intense broad absorption band in the NIR region at 850 nm are
assigned to polarons and bipolarons, respectively. The absorption
peak at 420 nm reveals electron transition from valence band to
anti-bipolaron band and the absorption beyond 850 nm is due to
electron transition from the valance band to the bipolaron band
[19]. The absorption in the NIR region, called the free carrier tail, is
known to reflect the delocalized conjugation length, i.e., the length
of an intramolecular conduction path of a polymer chain [19,20].
The electronic structure of PPy-DEHS prepared at low temperature
is similar to the standard PPy-DEHS reported previously [17].
Light scattering results (Fig. 2) show that an effective disper-
sion of the PPy was obtained in DCAA. The polymer was present
as a colloidal suspension with particle sizes <10 nm. Comparison of
particle sizes obtained from the standard PPy-DEHS (<100 nm) with
low temperature PPy-DEHS show that the conditions of polymer-
ization substantially decrease particle size due to an improvement
in solubility. Up to 25 wt% of low temperature PPy-DEHS could be
Table 1
Comparison of the elemental analysis of PPy-DEHS in as-synthesized powder form and after fibre spinning.
Elemental analysis (wt%)
Sample C H N S
Standard PPy powder 61.55 5.71 8.54
Low temp. powder 59.89 7.13 7.34
Undrawn PPy fibre 58.34 5.54 9.10
Drawn PPy fibre 61.80 6.02 9.60
1839
Fig. 3. TGA patterns of standard and low temperature PPy powder, PPy without
DEHS and dopant DEHS as a labeled.
suspended in DCAA, whereas only 10 wt% of standard PPy-DEHS
could be suspended in the same solvent.
Thermal stability of the chemical polymerized PPy-DEHS pow-
der and DEHS dopant were studied by TGA to 600 ◦ C under nitrogen
(Fig. 3). TGA shows a weight loss at ∼250–300 ◦ C of ∼44% and ∼55%
for PPy-DEHS prepared by the standard and low temperature meth-
ods, respectively. DEHS decomposes at ∼250 ◦ C. For comparison, the
thermal stability of a third polymer was evaluated. This third PPy
had been chemically polymerized using APS oxidant without DEHS.
This material showed no sharp reduction in mass at 250–300 ◦ C. It
is, therefore, expected that the weight loss in the PPy-DEHS samples
at 250–300 ◦ C is principally due to the decomposition of the DEHS
dopant. Since the low temperature PPy showed a higher weight loss
than standard PPy, these results support the conclusion that the
level of dopant is higher in low temperature PPy than in standard
PPy.
Elemental analysis of standard and low temperature PPy fibre
and powder were compared and the results are summarized in
Table 1. The as-synthesized low temperature PPy powder shows
a higher degree of doping with a sulfur to nitrogen atomic ratio
(S/N) of 33%, compared to the standard PPy powder with S/N = 26%.
Fibre spinning of the low temperature PPy-DEHS from DCAA solu-
tion resulted in a significant decrease in S level and the appearance
of a large Cl content. These results suggest that the DCAA (contain-
ing Cl) replaces some of the DEHS as co-dopant. There is also likely
to be residual DCAA solvent trapped in the as-spun fibre. Heating
the as-spun PPy fibres during the hot drawing process removed
some DCAA solvent from the polymer reducing the Cl/N ratio from
21% to 12%. The overall dopant level in the PPy-DEHS did not change
significantly and remained at about 30% in all cases.
3.2. PPy solution viscometry
A range of rheological tests have been used to estimate the
molecular weight of low temperature and standard PPy. The specific
viscosity of low temperature PPy solution as a function of PPy con-
centration is given in Fig. 4. The results are typical of those found
in polyelectrolyte solutions and polyaniline solutions [21–23]. At
higher concentrations the separation distance between individual
polymer chains is small and hence any significant diffusion of the
counter-anion away from its polymer chain due to the entropy
Atomic ratio
Cl C/H S/N Cl/N Doping %
5.05 – 0.90 0.26 – 26
5.56 – 0.70 0.33 – 33
3.48 4.81 0.88 0.17 0.21 37
4.22 2.70 0.86 0.19 0.12 30
1840 J. Foroughi et al. / Synthetic Metals 159 (2009) 1837–1843
Fig. 4. Specific viscosity of low temperature PPy in DCAA as a function of polymer
concentration. The inset shows the specific viscosity over a broader concentration
range.
effect is insignificant. Dilution, at first, therefore induces no signif-
icant change in molecular conformation and the specific viscosity
decreases, as expected, due to the smaller interaction between indi-
vidual polymer chains. At still lower concentrations, the diffusion
of DEHS− and/or DCAA− ions away from the positively charged
polymer chain increases due to entropy effects, with concomitant
chain expansion as evidenced by the increase in specific viscos-
ity [24]. In dilute solutions, the presence of ions either from the
self-ionization of DEHS− Na+ and/or DCAA or from trace impurities
becomes increasingly important, resulting in a screening effect as
Avlyanov and co-workers reported for PAni [21] with a resulting
decrease in specific viscosity.
Fig. 5 shows the reduced viscosity of PPy determined at differ-
ent solution concentrations. As can be seen, the reduced viscosity
of PPy in DCAA decreases linearly with increasing concentration.
The intrinsic viscosity [] is obtained by extrapolating data to zero
concentration. Therefore, according to Fig. 5 the intrinsic viscosity
of low temperature and standard PPy are [] = 3.25 and [] = 0.42
at 20 ◦ C, respectively. These results clearly demonstrate that the
low temperature PPy has a higher average molecular weight than
the standard PPy. Mark–Houwink–Sakurada (k, ˛) constants are not
available for PPy-DEHS in DCAA, so it is not possible to determine
the absolute molecular weight. The ratio of molecular weights will
be given by
 1/˛
Mlow temp. []low temp.
=
MSta. []Sta.
An approximate estimate of the ratio of molecular weights for
the low temperature and standard PPy can be obtained by using
˛ values that are typical of polyelectrolyte polymers in solution.
Fig. 5. Reduced viscosity of (a) low temperature polymerized PPy; and (b) standard
PPy in DCAA as a function of polymer concentration.
Fig. 6. The effect of different polymerization temperatures on the viscosity of the
spinning solutions (18%, w/w) of PPy dissolved in DCAA as a function of shear rate.
These ˛ values are in the range 0.5 < ˛ < 1. Using this range of ˛
values and the measured intrinsic viscosities, it is expected that
the low temperature PPy would have a molecular weight of 7–50
times larger than the standard PPy [25,26].
An understanding of the rheological properties of spinning solu-
tions can be used to determine the optimum conditions for wet
spinning. Fig. 6 shows the viscosity versus shear rate plots obtained
from high concentration solutions obtained from PPy-DEHS pre-
pared from the two different polymerization conditions. As can be
seen, increase of shear rate for both solutions generally decreases
the viscosity. However, the viscosity of low temperature PPy is sig-
nificant higher than standard PPy at all shear rates. This difference
reaches about ∼60 times in the low shear rate regime.
3.3. PPy fibre properties
Fibres were successfully spun from low temperature PPy DCAA
solution into long lengths. SEM micrographs of the PPy fibres are
given in Fig. 7. As can be seen from the SEM images, the fibres were
uniform in shape. Examination of the fibre cross-section (fracture
surface) showed the fibres to be dense and non-porous (Fig. 7d–f).
The surface morphology was slightly rough but again, pore-free
(Fig. 7b and c). The fibres were sufficiently flexible and tough to
tie into loose knots (Fig. 7a). Standard PPy fibres could not be tied
into tight knots without fracturing, although the morphology of
standard PPy fibres has previously been reported to be dense and
pore-free [14].
Polypyrrole powder gave rise to X-ray diffraction spectra that
exhibited a broad distribution of scattered intensity around 2 = 22◦
which has previously been related to the diffraction of amorphous
polypyrrole [27]. The shape and intensity of this scattering have
previously been reported to be highly dopant anion dependent
[28]. High-angle peaks around 2 = 22◦ , which are usually present
in polypyrrole, correspond to lattice d-spacings ranging from about
0.34 to 0.44 nm [28–30]. These peaks could be assigned to scat-
ter from PPy chains at spacings close to the interplanar van der
Waals distance for aromatic groups [31]. Low temperature PPy and
standard PPy showed very similar peak positions, reflecting a sim-
ilar level of molecular ordering. The scattering intensity at 22◦ was
higher for the low temperature PPy compared to the standard PPy,
which may be due to increased doping level in the former.
The thermo-mechanical properties of the as-spun fibers were
investigated to determine the optimal temperature for subsequent
mechanical drawing. According to the results given in Fig. 8, increas-
ing the temperature from 25 to 200 ◦ C causes the storage modulus
of as-spun PPy fibre to decrease from 2500 to 500 MPa. Fig. 8
also shows tan ı (E /E where E = storage modulus E = loss mod-
ulus) versus temperature data for the same undrawn fibre. There
 J. Foroughi et al. / Synthetic Metals 159 (2009) 1837–1843 1841

Fig. 7. SEM micrographs of low temperature PPy fibre at low and higher magnification showing the fibre cross-section (d–f) and surface (b and c).

is a small peak in the tan ı at ∼160 ◦ C where the storage modulus
decreases to 500 MPa. These results indicate a glass transition type
process occurs at ∼160 ◦ C. Truong et al. reported [32] that the glass
transition (Tg ) of PPy film doped with p-toluenesulfonate (pTS) is
∼155 ◦ C. A second, broad, tan ı peak was located at ∼70 ◦ C, which
may be related to secondary relaxations involving smaller molecu-
lar segments. Mechanical drawing requires large scale orientation
of polymer molecules, so drawing should be conducted near the Tg
where “whole chain” motion becomes possible.
Mechanical drawing of the as-spun low temperature PPy fibres
was conducted at 100 ◦ C. The drawing was conducted at a controlled
displacement rate to a total strain of 40%. As shown in Fig. 9, the
stress–strain diagram during drawing at 100 ◦ C displayed a distinct
yield at approximately 15 MPa and 5% strain. The fibres were drawn
to 40% strain without failure and then unloaded and cooled to room
temperature for further evaluation.
The mechanical properties tested at room temperature of as-
spun PPy fibres are given in Fig. 10. Stress–strain curves obtained
from as-spun standard and as-spun low temperature PPy fibres

Fig. 8. Storage modulus of undrawn PPy fibre and tan ı (ı = E /E where E = storage Fig. 9. Stress–strain curve during stretching at ∼100 ◦ C for low temperature PPy
modulus E = loss modulus) of undrawn PPy fibre vs. temperature. fibre. The test was terminated at 40% strain without failure in the fibre.
1842 J. Foroughi et al. / Synthetic Metals 159 (2009) 1837–1843
Fig. 10. Stress–strain curves obtained from room-temperature tensile testing of PPy
fibres as labeled.
show a significant increase in ductility of the latter. Analysis of
these curves indicates a stress at break ∼65 MPa with ∼8% strain for
low temperature PPy compared with only ∼27 MPa stress with ∼2%
strain for standard PPy. Young’s modulus of these PPy fibres was ∼3
and ∼1.5 GPa for low temperature and standard PPy fibres, respec-
tively. It is expected that the higher molecular weight produced by
the low temperature polymerization reduces the brittleness and
allows a higher ductility than occurs in the standard PPy. The higher
modulus found in the low temperature PPy may reflect a greater
degree of molecular ordering, although XRD results were not con-
clusive in this regard.
A comparison of the room-temperature mechanical properties
of undrawn (as-spun) and drawn low temperature PPy fibres are
also given in Fig. 10. The drawn low temperature PPy sample shows
significantly increased Young’s modulus and strength compared to
the undrawn fibre. After drawing to 40% at 100 ◦ C, the Young’s mod-
ulus increased to 4.2 GPa and the breaking strength was 136 MPa. A
small reduction in breaking strain (to 5%) was also noted.
Electrical conductivity and electroactivity of low temperature
PPy fibres was also determined. The average electrical conductiv-
ity of undrawn low temperature PPy fibres was measured to be
∼3 S cm−1 . The conductivity is similar to that previously obtained
for PPy films cast with this dopant [26] from DMF and NMP solution
and standard PPy fibres [17]. However, drawing of low temperature
drawn PPy fibres to 40% strain at 100 ◦ C increased the electrical con-
ductivity to 30 S cm−1 . Similar increases in conductivity have been
reported upon drawing of PPy-DEHS cast films [1]. The elongated
coil structure formed during drawing likely increases the overlap
of pi-orbitals and thereby increases intra-chain conductivity.
Cyclic voltammetry for the drawn PPy fibre in electrolyte (0.1 M
DEHS dissolved in acetonitrile–water 1:1) is shown in Fig. 11.
Reasonable electroactivity was observed in the PPy fibres as evi-
denced by oxidation and reduction peaks at ∼0 and −0.5 V (Ag/AgCl
reference), respectively. The redox activity was reasonably sta-
ble for up to 100 cycles. The reduction process in these drawn
Fig. 11. Cyclic voltammogram of drawn PPy fibre potential was scanned between
−0.9 V and +0.6 V (vs. Ag/AgCl) in 0.1 M DEHS in acetonitrile/water (1:1) at
100 mV s−1 .
PPy fibres occurs at lower potentials than previously reported for
electrochemically prepared films of PPy doped with dodecylben-
zenesulfonic acid (−0.3 to +0.1 V, vs. Ag/AgCl for the reduction
potential [33]). The differences in redox potentials probably reflects
the influence of the dopant as well as possible differences in molec-
ular weight, cross-linking and molecular order. The electroactivity
and electrical conductivity observed in these fibres suggests that
the fibres may be useful for sensors, actuators and batteries as
previously shown for polyaniline fibres [34–36].
4. Conclusions
Polypyrrole fibres with improved properties have been pro-
duced. A low temperature polymerization process enabled the
formation of highly soluble non-functionalised PPy using DEHS
dopant as originally reported by Oh et al. [16]. This soluble material
could then be spun into fibres [17]. The low temperature polymer-
ization gave higher molecular weight PPy with a higher doping level
that the standard 0 ◦ C polymerization. The fibres were sufficiently
robust to be able to be drawn to 40% strain at 100 ◦ C. The resultant
mechanical strength of drawn fibres was 136 MPa, and modulus
was 4.2 GPa. The fibres were electroactive with a conductivity of
30 S cm−1 in the drawn state.
Acknowledgements
The authors gratefully acknowledge the financial support of the
Australian Research Council through its Centres of Excellence Pro-
gram.
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